JP7462758B2 - Surfactants for cleaning products - Google Patents

Description

CROSS-REFERENCE TO RELATED APPLICATIONS This application claims priority to U.S. Provisional Patent Application No. 62/951,942, filed December 20, 2019, the disclosure of which is incorporated herein by reference in its entirety.

FIELD The present disclosure relates to surfactants for use in cleaning products, including cleaning products used to clean and condition textiles, hard surfaces, and plastic surfaces. Such surfactants may include siloxane derivatives of amino acids, which have surface active properties.

Surfactants (molecules with surface active properties) are used widely in commercial applications in formulations ranging from detergents to hair care products to cosmetics. Compounds with surface active properties are used as soaps, detergents, lubricants, wetting agents, foaming agents, and spreading agents, among others. In personal care cleaning products (e.g., shampoos, body washes, facial cleansers, liquid hand soaps, etc.), surfactants are often the most important ingredient since they provide many of the cleaning attributes of the composition.

Surfactants may be uncharged, zwitterionic, cationic, or anionic. In principle, any surfactant class (e.g., cationic, anionic, nonionic, amphoteric) is suitable for cleaning or cleaning applications, but in practice many personal care cleaners and household cleaning products are formulated with a combination of two or more surfactants from two or more surfactant classes.

Surfactants are often amphiphilic molecules with a relatively water-insoluble hydrophobic "tail" group and a relatively water-soluble hydrophilic "head" group. These compounds can be adsorbed at interfaces, such as those between two liquids, between a liquid and a gas, or between a liquid and a solid. In systems that contain a relatively polar component and a relatively non-polar component, the hydrophobic tail interacts preferentially with the relatively non-polar component(s) and the hydrophilic head interacts preferentially with the relatively polar component(s). In the case of an interface between water and oil, the hydrophilic head group preferentially extends into the water and the hydrophobic tail preferentially extends into the oil. When added to a water-gas only interface, the hydrophilic head group preferentially extends into the water and the hydrophobic tail preferentially extends into the air. The presence of the surfactant disrupts at least some of the intermolecular interactions between the water molecules, replacing them with generally weaker interactions between at least some of the water molecules and the surface active agent. This results in reduced surface tension and can help stabilize the interface.

At high enough concentrations, surfactants may form aggregates that help limit the exposure of the hydrophobic tails to polar solvents. One such aggregate is a micelle. In a typical micelle, the molecules are arranged in a sphere such that the hydrophobic tails of the surfactant(s) are preferentially located inside the sphere and the hydrophilic heads of the surfactant(s) are preferentially located on the outside of the micelle, where the heads preferentially interact with the more polar solvent. The effect of a given compound on surface tension and the concentration at which it forms micelles can serve as defining characteristics of a surfactant.

The present disclosure provides compositions for cleaning and/or degreasing hard and plastic surfaces such as floors, walls, ceilings, roofs, countertops, furniture, boards, cups, glass, cutlery, tableware, machinery, machine parts, and devices used in food preparation and/or packaging; textile care formulations including laundry detergents, stain removers, cleaning pre-treats, fabric softeners, fabric dyes, and bleaches; and compositions used to clean upholstery and carpets. Some of the compositions of the present invention may be in the form of detergents, emulsifiers, dispersants, foaming agents, and combinations thereof. The products of the present invention may be formulated to include one or more surfactants from one or more surfactant classes.

The present disclosure provides siloxane derivatives of amino acids having surface active properties. The amino acids may be naturally occurring or synthetic amino acids, or they may be obtained via ring-opening reactions of molecules such as lactams, e.g., caprolactam. The amino acids may be functionalized with different types of siloxane groups to form compounds having surface active properties. Characteristically, these compounds may have a low critical micelle concentration (CMC) and/or the ability to reduce the surface tension of liquids.

The present disclosure relates to the following formula 1

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from hydrogen, oxygen, hydroxyl, and C ₁ -C 6 alkyl. ₆ alkyl), where an optional counterion may be associated with the compound, and where the counterion, if present, may be selected from the group consisting of chloride, bromide, and iodide, and one or more soaps which may themselves be characterized as surfactants, the soaps may include fatty acids, salts, and some soaps may include both water soluble and fat soluble portions.

Further compounds provided by the present disclosure are represented by formula 1a

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; m is an integer from 1 to 6; the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from hydrogen, oxygen, and C ₁ -C 6 alkyl. ₆ alkyl, the alkyl chain optionally being substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; an optional counterion may be associated with the compound, the counterion, if present, may be selected from the group consisting of chloride, bromide, and iodide; and at least one builder may comprise a molecule that promotes the effectiveness of the cleaning action in an aqueous environment; some useful builders include, but are not limited to, certain polymers, phosphates, and aluminosilicates, calcium citrate, alkali metal salts, sodium salts, and some grades of zeolites.

Additional compounds provided by the present disclosure are represented by formula 1

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; p is 5; the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from hydrogen, oxygen, and C ₁ -C 6 alkyl. ₆ alkyl, wherein the alkyl chain is optionally substituted with one or more substituents selected from the group consisting of carboxyl, carboxylate, and sulfonate; an optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide; and bleaching agents, such as peroxy bleaches, include, but are not limited to, inorganic peroxy base salts, organic peroxy acids, metal borates, percarbonates, perphosphates, persilicates, and persulfates.

The present disclosure relates to the following formula 1

wherein R ¹ and R ² may be the same or different and may contain at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may contain one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; and the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C ₁ -C ₆ alkyl, an optional counterion may be associated with the compound, and the counterion, if present, may be selected from the group consisting of chloride, bromide, and iodide, and a non-flammable oil-immersion composition that is preferred as a solvent, and optionally a co-solvent, for use in either or both domestic or commercial dry cleaning processes.

Still other compounds provided by the present disclosure are those compounds of formula 1 where R ¹ and R ² are methyl.
Another compound provided by the present disclosure is that of formula 1, where n is 5.

Yet another compound provided by the present disclosure is that of formula 1b, where R ¹ and R ² are methyl.
Yet another compound provided by the present disclosure is that of formula 1, wherein R ³ is hydrogen.

Another compound provided by the present disclosure is a compound of Formula 1, wherein the counterion is selected from the group consisting of chloride, bromide and iodide.
An additional compound provided by the present disclosure is that of formula 1b, where the counterion is chloride.

Another compound provided by the present disclosure is a compound of formula 1 where R ³ is methyl.
Another compound provided by the present disclosure is that of formula 1, where the counterion is iodide.

Yet another compound provided by the present disclosure is that of formula 1, where R ³ is oxygen.
Additional compounds provided by the present disclosure are those of formula 1 where R ³ is C ₁ -C ₆ alkyl substituted with a sulfonate.

One specific compound provided by the present disclosure has the following formula:

6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)hexanamide.

The second specific compound provided by the present disclosure has the following formula:

6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)hexaminium chloride.

A third specific compound provided by the present disclosure has the following formula:

36-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide.

A fourth specific compound provided by the present disclosure has the following formula:

6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-amine oxide.

A fifth specific compound provided by the present disclosure has the following formula:

It is 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate.

A sixth specific compound provided by the present disclosure has the following formula:

5-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)pentane-1-sulfonate.

The above and other features of the present disclosure, as well as the manner in which they are realized, will become more apparent and better understood by reference to the following description of the embodiments taken in conjunction with the accompanying drawings.

FIG. 1 shows a plot of surface tension versus concentration for Surfactant 2, with a chloride counterion measured at pH=7, as described in Example 1b. FIG. 2 shows a plot of surface tension versus concentration for Surfactant 3, as described in Example 2b. FIG. 3 shows a plot of dynamic surface tension versus time as the surface tension changes for Surfactant 3, as described in Example 2b. FIG. 4 shows a plot of surface tension versus concentration for Surfactant 4, as described in Example 3b. FIG. 5 shows a plot of dynamic surface tension versus time as the surface tension changes for Surfactant 4, as described in Example 3b. FIG. 6 shows a plot of surface tension versus concentration for surfactant 5, as described in Example 4b. FIG. 7 shows a plot of dynamic surface tension versus time as the surface tension changes for Surfactant 5, as described in Example 4b.

As used herein, the phrase "within any range defined between any two of the preceding values" literally means that any range may be selected from any two of the values listed before such phrase, regardless of whether the values are in the lower portion of the list or in the higher portion of the list. For example, a pair of values may be selected from two lower values, two higher values, or a lower value and a higher value.

The term "alkyl" as used herein means any saturated carbon chain which may be a straight chain or branched chain.
The phrase "surface active" as used herein means that the associated compound is capable of lowering the surface tension of the medium in which it is at least partially dissolved and/or the interfacial tension with other phases and thus may be at least partially adsorbed at liquid/vapor and/or other interfaces. The term "surfactant" may be applied to such compounds.

In relation to the terminology of imprecision, the terms "about" and "approximately" may be used interchangeably to refer to measurements that include the stated measurement and also include any measurement that is reasonably close to the stated measurement. A measurement that is reasonably close to the stated measurement deviates from the stated measurement by a reasonably small amount, as understood and readily ascertained by one of ordinary skill in the relevant art. Such deviations may be due, for example, to measurement error or minor adjustments made to optimize performance. In cases where it is determined that one of ordinary skill in the relevant art would not readily ascertain values for such reasonably small differences, the terms "about" and "approximately" may be understood to mean plus or minus 10% of the stated value.

Unless expressly defined or otherwise implicit, the term "foam" as used herein refers to a non-equilibrium dispersion of gas bubbles in a relatively smaller volume of liquid. Terms such as "foam," "foam," and "bubbles" may be used interchangeably within the meaning of the present invention.

Unless otherwise expressly defined or otherwise implicitly used, the term "suds profile" as used herein refers to a property of a detergent composition that relates to the characteristics of foam during the wash and rinse cycles. The suds profile of a detergent composition includes, but is not limited to, the rate of foam generation upon dissolution in the wash liquor, the foam volume and retention during the wash cycle, and the foam volume and disappearance during the rinse cycle. Preferably, the suds profile includes a Wash Suds Index and a Rinse Suds Index specifically defined by the test methods disclosed in the Examples hereinafter. It may further include additional suds-related parameters such as foam stability measured during the wash cycle, and the like.

Unless expressly defined or implicitly used otherwise, the term "fluid" as used herein encompasses liquid, gel, paste and gas product forms.
Unless expressly defined otherwise or implicitly used, the term "liquid" as used herein refers to a fluid having a viscosity of about 1 to about 2000 mPa ^* s at 25° C. and a shear rate of 20 sec-1.

Unless otherwise expressly stated or implied, the term "dry cleaning composition" as used herein means the composition used in the dry cleaning process, including the dry cleaning solvent, any surfactants, and cleaning agents, excluding the laundry to be cleaned.

Unless expressly defined or implicitly used otherwise, the term "organic dry cleaning solvent" as used herein shall mean any non-aqueous solvent having a liquid phase, preferably at 20° C. and standard pressure. The term organic has its usual meaning, i.e., a compound having at least one carbon-hydrogen bond.

The present disclosure provides compositions for cleaning and/or degreasing hard and plastic surfaces such as floors, walls, ceilings, roofs, countertops, furniture, boards, cups, glass, cutlery, tableware, machinery, machine parts, and devices used in food preparation and/or packaging; textile care formulations including laundry detergents, stain removers, cleaning pre-treats, fabric softeners, fabric dyes, and bleaches; and compositions used to clean upholstery and carpets.

I. Water-Based Cleaning Formulations Laundry detergents, degreasers, stain removers, and laundry pre-treatment compositions may contain combinations of detergent surfactants, binders, enzymes, and conditioning agents. Laundry detergent formulations include solids, liquids, powders, bars, sticks, pods, aerosols, and/or gels.

The laundry detergent compositions of the present invention may be used in automatic machine wash, semi-automatic appliance wash (i.e., machine wash requiring at least one or two manual steps), hand wash, and other applications. In some embodiments, the detergent composition is designated as a hand wash laundry detergent product.

The laundry detergent composition can be in any form, i.e., liquid; emulsion; paste; gel; spray or foam; solid, such as powder, granule, agglomerate, tablet, pouch, and bar; delivered in a bi-compartment or multi-compartment container or pouch; pre-moistened or dry wipes that can be activated by the consumer with water (i.e., liquid detergent composition combined with a nonwoven material, or powder detergent composition combined with a nonwoven material); and other homogeneous or multi-layered consumer cleaning product forms.

Some of the fabric care formulations of the present invention include one or more surfactants, also referred to as a surfactant system. The surfactant system is included to provide cleaning performance to the composition. The surfactant system includes at least one surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, and optionally at least one other surfactant, which may be an amphoteric surfactant, a zwitterionic surfactant, a cationic surfactant, a nonionic surfactant, or a combination thereof. Such surfactants must be physically and chemically compatible with the essential ingredients described herein or otherwise not impart excessive product stability, cosmetic properties, or performance.

The compositions of the present invention may be in any suitable physical form, such as particulates (powder, granules, tablets), liquids, pastes, gels or bars. Preferably, the detergent compositions are in granular form. The compositions may be formulated for use as hand or machine wash detergents.

A representative, non-limiting laundry detergent formulation may include a combination of soap, ionic surfactants, nonionic surfactants, optionally a builder system, and optionally other detergent ingredients, where a set amount of soap is present in the form of granules that are dry mixed with the other ingredients, the soap granules having a predetermined concentration of soap.

Some preferred detergent compositions according to the present invention exhibit improved dissolution characteristics within a range of water hardnesses.
1. Detergents and/or Soaps Detergents include anionic, cationic, nonionic, and zwitterionic detergents. Soaps include compounds of the general formula: (RCO ₂ ⁻ ) _n M ⁿ⁺ , where R is an alkyl group, M is a metal, and ⁿ⁺ is either +1 or +2, commonly the alkyl group may be part of a fatty acid, and M may be sodium, lithium, magnesium, calcium, and the like.

The soap according to the invention may constitute about 5-85 wt %, preferably 7-60 wt %, more preferably 10-35 wt % of the formulation. The soap may include, in part, a surfactant system which constitutes about 20-50 wt % of the soap. Preferably, the surfactant system constitutes 30-40 wt % of the soap. In a preferred embodiment of the invention, 80 wt % to 100 wt %, preferably 85-95 wt % of the soap is present in the form of granules.

The laundry detergent compositions of the present invention may comprise soap granules having a soap concentration of at least 75 wt% based on the weight of the composition.
In some embodiments of the present invention, the soap granules have a soap concentration of 80-95 wt%, preferably 85-90 wt%. Preferably, the soap granules contain more than 90 wt% soap, less than 10 wt% water, and less than 1 wt% sodium hydroxide.

Useful soap compounds include, but are not limited to, alkali metal soaps such as the sodium, potassium, ammonium and substituted ammonium (e.g., monoethanolamine) salts of higher fatty acids containing about 8 to 24 carbon atoms, or any combination thereof.

In some embodiments of the present invention, the fatty acid soap has a carbon chain length of _C10 - _C22 , more preferably _C12 - _C20 . Suitable fatty acids can be obtained from natural sources such as vegetable or animal esters, for example palm oil, coconut oil, babassu oil, soybean oil, castor oil, rapeseed oil, sunflower oil, cottonseed oil, tallow, fish oil, grease lard, and mixtures thereof. Fatty acids can also be produced by synthetic means such as oxidation of petroleum or hydrogenation of carbon monoxide by the Fischer-Tropsch process. Resin acids such as rosin and their resin acids in tall oil are suitable. Naphthalene acid is also suitable. Sodium and potassium soaps can be made by direct saponification of fats and oils or by neutralization of free fatty acids prepared in a separate manufacturing process. Particularly useful are the sodium and potassium salts of fatty acids derived from coconut oil and tallow, and mixtures thereof, i.e. sodium tallow soap, sodium coconut soap, potassium tallow soap, potassium coconut soap.

In some embodiments of the present invention, the fatty acid soap is a lauric acid soap, such as Prifac 5908 fatty acid from Uniqema neutralized with caustic soda. This soap is an example of a fully hydrogenated or saturated lauric acid soap, typically based on coconut or palm kernel oil.

Preferably, but not necessarily, the soap does not protrude from the rest of the ingredients. It should therefore be whitish in colour and somewhat round, i.e. have an aspect ratio of less than 2. This ensures that the final form of the laundry powder flows well and that, if it contains soap granules, they will blend in with the rest of the composition.

In one preferred embodiment, the soap has a particle size of 400 to 1400 μm, preferably 500 to 1200 μm.
In one preferred embodiment, the soap granules have a bulk density of 400-650 g/l, and the bulk density of the fully formulated powder is 400-900 g/l. Fabric washing powders containing high amounts of soap are preferred by some consumers because they tend to leave fabrics feeling softer than those washed with powders based on synthetic detergent active compounds, with good cleaning power. Soap also has environmental benefits in that it is fully biodegradable and is a natural material derived from renewable sources. Saturated sodium soaps have a high Kraft temperature and, as a result, only slightly soluble at the low temperatures applied by some consumers. It is well known that certain mixtures of saturated and unsaturated soaps have fairly low Kraft temperatures. However, unsaturated soaps tend to be less stable and malodorous on storage. The soap mixtures used in the granules must therefore be carefully balanced between solubility and stability properties. The stability of the soap is enhanced when the soap is concentrated in the granules compared to soaps incorporated at low concentrations in the complex granules. The soap may be used in combination with a suitable antioxidant, such as ethylenediaminetetraacetic acid and/or ethane-1-hydroxy-1,1-diphosphonic acid. Preservatives that may be present to prevent soap degradation, such as sodium hydroxyethylidene diphosphonate, can also be rancid or discolour.

2. Surfactants Surfactants that can be used to practice aspects of the present invention are represented by the following formula 1:

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C ₁ -C ₆ alkyl, and an optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

Anionic surfactants are well known to those skilled in the art. Examples include alkyl benzene sulfonates, especially linear alkyl benzene sulfonates with alkyl chains of Cs to Cs, primary and secondary alkyl sulfonates, especially Cs to Co primary alkyl sulfates; alkyl ether sulfates; olefin sulfonates; alkyl xylene sulfonates; dialkyl sulfosuccinates; and fatty acid ester sulfonates. Sodium salts are generally preferred. According to a preferred embodiment of the present invention, the granular laundry detergent composition comprises an anionic surfactant which is a sulfonate anionic surfactant. According to a particularly preferred embodiment, the sulfonic acid anionic surfactant comprises linear alkyl benzene sulfonate (LAS). In a preferred embodiment, the anionic surfactant is present in an amount of 15 to 50 wt %. In a preferred embodiment, the weight ratio of anionic surfactant to soap is 0.5:1 to 5:1, preferably 1:1 to 2:1.

Some nonionic surfactants (iii) are well suited for use in detergent formulations.
In some embodiments, the nonionic surfactant is present in an amount of 20 to 60 wt %. Nonionic surfactants that may be used include primary and secondary alcohol ethoxylates, particularly C8 to C20 fatty alcohols ethoxylated with an average of 1 to 20 moles of ethylene oxide per mole of alcohol, more particularly C10 to C15 primary and secondary fatty alcohols ethoxylated with an average of 1 to 10 moles of ethylene oxide per mole of alcohol. Non-ethoxylated nonionic surfactants include alkyl polyglycosides, glycerol monoethers, and polyhydroxyamides (glucamides).

Examples of suitable nonionic surfactants include Neodol 255E from Shell, which is a C12-C15 poly(1-6) ethoxylate with an average degree of ethoxylation of 5. Also suitable is Lutensol A7, a C13-C15 ethoxylate from BASF with an average degree of ethoxylation of 7. HLB values can be calculated according to the method given in Griffin, J. Soc. Cosmetic Chemists, 5 (1954) 249 258.

3. Builders Builders may be added to detergent formulations to enhance the cleaning properties of the detergent. Such compounds may function by at least one of the following actions: scavenging or sequestering divalent cations, commonly present in water as Ca2+ and/or Mg2+; creating or contributing to the creation of an alkaline environment; enhancing surfactant performance; and stabilizing the dispersion of soils in the wash liquor.

Commonly used builders include, but are not limited to, sodium tripolyphosphate, nitriloacetate, and zeolites.
The compositions of the present invention may contain a detergent builder. Preferably the builder is present in an amount of 0 to 15 wt %, based on the weight of the total composition. Alternatively the compositions may be essentially free of detergent builders.

The builder may be selected from strong builders such as phosphate builders, aluminosilicate builders, and mixtures thereof. One or more weak builders such as calcite/carbonate, citrate, or polymer builders may additionally or alternatively be present.

The phosphate builder, if present, may be selected, for example, from alkali metal, preferably sodium, pyrophosphates, orthophosphates and tripolyphosphates, and mixtures thereof.

The aluminosilicate (if present) may be selected from, for example, one or more crystalline and amorphous aluminosilicates, such as the zeolites disclosed in GB 1 473 201 (Henkel), the amorphous aluminosilicates disclosed in GB 1 473 202 (Henkel), and the crystalline/amorphous aluminosilicate mixtures disclosed in GB 1 470 250 (Procter &Gamble); and the layered silicates disclosed in EP 164 514 (Hoechst).

The alkali metal aluminosilicate may be either crystalline or amorphous, or a mixture thereof, having the general formula: 0.8-1.5Na ₂ O·Al ₂ O ₃ ·0.8-6SiO ₂ .

These materials may generally contain some bound water and should have a calcium ion exchange capacity of at least 50 mg CaO/g. Preferred sodium aluminosilicates contain 1.5-3.5 _SiO2 units (in the formula above). Both amorphous and crystalline materials may be readily prepared by reaction of sodium silicate with sodium aluminate, as is widely described in the literature. Suitable crystalline sodium aluminosilicate ion exchange detergent builders are described, for example, in GB 1 429 143 (Procter & Gamble). Preferred sodium aluminosilicates of this type are the well-known commercially available zeolites A and X, and mixtures thereof.

The zeolite may be the commercially available Zeolite 4A, which is currently widely used in laundry detergent powders. However, according to a preferred aspect of the invention, the zeolite builder incorporated in the compositions of the invention is Maximum Aluminum Zeolite P (Zeolite MAP) as described and claimed in EP 384070 (Unilever). Zeolite MAP is defined as an alkali metal aluminosilicate of the Zeolite P type having a silicon to aluminum ratio not exceeding 1.33, preferably within the range of 0.90 to 1.33, more preferably within the range of 0.90 to 1.20.

Suitable inorganic salts include alkaline agents such as alkali metals, preferably sodium, carbonates, sulfates, silicates, metasilicates, either as individual salts or as double salts. The inorganic salts may be selected from the group consisting of sodium carbonate, sodium sulfate, burkeite, and mixtures thereof.

4. Surface Active Ingredients In addition to the surfactants and builders discussed above, the compositions may optionally contain other active ingredients that enhance performance and properties.

Additional detergent-active compounds (surfactants) may be selected from soap and non-soap anionic, cationic, nonionic, amphoteric and zwitterionic detergent-active compounds and mixtures thereof. Many suitable detergent-active compounds are available and are fully described in the literature, for example in "Surface-Active Agents and Detergents", Volumes I and II by Schwartz, Perry and Berch.

Cationic surfactants that may be used include quaternary ammonium salts of the general formula RRRRNX, where the R group is a long or short chain hydrocarbyl chain, typically an alkyl, hydroxyalkyl or ethoxylated alkyl group, and X is a solubilizing anion (e.g., compounds in which R is a C8-C22 alkyl group, preferably a C8-C10 or C12-C14 alkyl group, R is a methyl group, and R and R may be the same or different and are methyl or hydroxyethyl groups) and cationic esters (e.g., choline esters).

Amphoteric and/or zwitterionic surfactants may also be present. Some amphoteric surfactants that may be used to practice the present invention include amine oxides.

Some zwitterionic surfactants that can be used to practice the present invention include betaines, such as amidobetaines.
5. Bleaching Agent The detergent composition according to the present invention may suitably contain a bleaching agent system. The bleaching agent system is preferably based on a peroxy bleaching compound, for example an inorganic persalt or an organic peroxy acid capable of generating hydrogen peroxide in aqueous solution. Suitable peroxy bleaching compounds include organic peroxides such as urea peroxide, and inorganic persalts such as alkali metal perborates, percarbonates, perphosphates, persilicates and persulfates. Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate. Particularly preferred is sodium percarbonate with a protective coating against destabilization by moisture. Sodium percarbonate with a protective coating containing sodium metaborate and sodium silicate is disclosed in GB 2123044 (Kao).

The peroxy bleach compound is suitably present in an amount of from 5 to 35 wt %, preferably from 10 to 25 wt %.
The peroxy bleach compounds may be used in conjunction with a bleach activator (bleach precursor) to improve bleaching action at low water temperatures. The bleach precursor is suitably present in an amount of 1 to 8 wt %, preferably 2 to 5 wt %.

Preferred bleach precursors are peroxycarboxylic acid precursors, more particularly peracetic acid precursors and peroxybenzoic acid precursors; and peroxycarbonic acid precursors. A particularly preferred bleach precursor suitable for use in the present invention is N,N,N',N'-tetraacetylethylenediamine (TAED). Also of interest are peroxybenzoic acid precursors, particularly N,N,N-trimethylammonium toluoyloxybenzenesulfonate.

A bleach stabilizer (heavy metal sequestrant) may also be present. Suitable bleach stabilizers include ethylenediaminetetraacetate (EDTA) and polyphosphonates such as Dequest™, EDTMP, etc.

6. Enzymes The detergent composition may also contain one or more enzymes. Suitable enzymes include, for example, proteases, amylases, cellulases, oxidases, mannanases, peroxidases, and lipases available for incorporation into the detergent composition. In particulate detergent compositions, detergent enzymes are commonly used in granular form in amounts of about 0.1 to about 3.0 wt %. However, any suitable physical form of the enzyme may be used in any effective amount.

7. Polymers Some detergents may include a cationic polymer. Cationic polymers such as those described below, when used in laundry detergent compositions in an amount ranging from about 0.01 wt % to about 15 wt %, are effective in improving the suds profile of such laundry detergent compositions compared to compositions of similar formulation but without such cationic polymer.

Cationic polymers useful in detergents, such as laundry detergents, include the following: The cationic polymer used in the present invention is a terpolymer containing three different types of structural units. It is substantially free, and preferably essentially free, of any other structural components. The structural units or monomers may be incorporated into the cationic polymer in a random or block fashion.

The first structural unit in the cationic polymer of the present invention is a nonionic structural unit derived from (meth)acrylamide (AAm). The cationic polymer contains about 35 mol% to about 85 mol%, preferably about 55 mol% to about 85 mol%, more preferably about 65 mol% to about 80 mol% of structural units derived from AAm.

The second structural unit in the cationic polymer is a cationic structural unit derived from any suitable water-soluble cationic ethylenically unsaturated monomer, such as, for example, N,N-dialkylaminoalkyl methacrylate, N,N-dialkylaminoalkyl acrylate, N,N-dialkylaminoalkyl acrylamide, N,N-dialkylaminoalkyl methacrylamide, methacrylamide alkyl trialkyl ammonium salt, acrylamido alkyl trialkyl ammonium salt, vinylamine, vinyl imidazole, quaternary vinyl imidazole, and diallyl dialkyl ammonium salt.

For example, the second cationic structural unit may be derived from a monomer selected from the group consisting of diallyldimethylammonium salt (DADMAS), N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate (DMAM), [2-(methacryloylamino)ethyl]trimethylammonium salt, N,N-dimethylaminopropylacrylamide (DMAPA), N,N-dimethylaminopropyl methacrylamide (DMAPMA), acrylamidopropyltrimethylammonium salt (APTAS), methacrylamidepropyltrimethylammonium salt (MAPTAS), and quaternary vinylimidazole (PVi), and combinations thereof.

In some embodiments, the second cationic structural unit is derived from a diallyldimethylammonium salt (DADMAS), such as, for example, diallyldimethylammonium chloride (DADMAC), diallyldimethylammonium fluoride, diallyldimethylammonium bromide, diallyldimethylammonium iodide, diallyldimethylammonium bisulfate, diallyldimethylammonium alkyl sulfate, diallyldimethylammonium dihydrogen phosphate, diallyldimethylammonium hydrogen alkyl phosphate, diallyldimethylammonium dialkyl phosphate, and combinations thereof. Alternatively, the second cationic structural unit may be derived from a [2-(methacryloylamino)ethyl]trimethylammonium salt, such as, for example, [2-(methacryloylamino)ethyl]trimethylammonium chloride, [2-(methacryloylamino)ethyl]trimethylammonium fluoride, [2(methacryloylamino)ethyl]trimethylammonium bromide, [2-(methacryloylamino)ethyl]trimethylammonium iodide, [2-methacryloylamino]ethyl]trimethylammonium bisulfate, [-(methacryloylamino)ethyl]trimethylammonium alkyl sulfate, [2-(methacryloylamino)ethyl]trimethylammonium dihydrogen phosphate, [2-(methacryloylamino)ethyl]trimethylammonium hydrogen alkyl phosphate, [2(methacryloylamino)ethyl]trimethylammonium dialkyl phosphate, and combinations thereof. Additionally, the second cationic structural unit may be derived from an APTAS such as, for example, acrylamidopropyltrimethylammonium chloride (APTAC), acrylamidopropyltrimethylammonium fluoride, acrylamidopropyltrimethylammonium bromide, acrylamidopropyltrimethylammonium iodide, acrylamidopropyltrimethylammonium bisulfate, acrylamidopropyltrimethylammonium alkyl sulfate, acrylamidopropyltrimethylammonium dihydrogen phosphate, acrylamidopropyltrimethylammonium hydrogen alkyl phosphate, acrylamidopropyltrimethylammonium dialkyl phosphate, and combinations thereof. Additionally, the second cationic structural unit may be derived from MAPTAS, such as, for example, methacrylamidepropyltrimethylammonium chloride (MAPTAC), methacrylamidepropyltrimethylammonium fluoride, methacrylamidepropyltrimethylammonium bromide, methacrylamidepropyltrimethylammonium iodine, methacrylamidepropyltrimethylammonium bisulfate, methacrylamidepropyltrimethylammonium alkyl sulfate, methacrylamidepropyltrimethylammonium dihydrogen phosphate, methacrylamidepropyltrimethylammonium hydrogen alkyl phosphate, methacrylamidepropyltrimethylammonium dialkyl phosphate, and combinations thereof.

The second cationic structural unit is present in the cationic polymer in an amount ranging from about 10 mol% to about 65 mol%, preferably from about 15 mol% to about 60 mol%, and more preferably from about 15 mol% to about 30 mol%.

The presence of a relatively large amount (e.g., about 65 mol% to about 80 mol%) of the first nonionic structural unit and a moderate amount (e.g., about 15 mol% to about 30 mol%) of the second cationic structural unit ensures good foaming benefits and good end product appearance. If the first nonionic structural unit is present at less than 65 mol% and the second cationic structural unit is present at more than 30 mol%, the foaming benefits or end product appearance will start to deteriorate, e.g., the rinse foam volume may increase significantly or the end product will no longer be transparent and will appear cloudy. Similarly, if the first nonionic structural unit is present at more than 85 mol% and the second cationic structural unit is present at less than 10 mol%, the rinse foam volume will increase to a level that is no longer acceptable for the purposes of the present invention.

The third structural unit in the cationic polymer is an anionic structural unit derived from (meth)acrylic acid (AA) or its anhydride. The cationic polymer may contain about 0.1 mol% to about 35 mol%, preferably 0.2 mol% to about 20 mol%, more preferably about 0.5 mol% to about 10 mol%, and most preferably about 1 mol% to about 5 mol% of the third anionic structural unit.

The presence of a relatively small amount (e.g., 1 mol % to 5 mol %) of the third anionic structural unit can help increase the hydrophilicity of the resulting polymer, which in turn can lead to better cleaning, especially better clay removal. Too many third anionic structural units (e.g., more than 30 mol %) can impair the foaming benefits of the resulting polymer.

II. Dry Cleaning According to some aspects of the present invention, a formulation for a dry cleaning process comprises a dry cleaning step in which laundry soiled with particulate soils is contacted with a dry cleaning composition having a liquor to cloth ratio (w/w) (LCR) of at most 20, said composition comprising:
a) a non-flammable, non-chlorine containing, organic dry cleaning solvent; and b) a cleaning effective amount of an acidic surfactant.
Provided for in-home dry cleaning.

In some embodiments, the dry cleaning step is a low-aqueous dry cleaning step, and the composition is a low-aqueous dry cleaning composition comprising 0.01-10 wt. % water.

According to yet another aspect of the invention, a dry cleaning process further includes a non-aqueous dry cleaning step in which the laundry is contacted with a non-aqueous dry cleaning composition comprising 0.001-10 wt % surfactant; 0-0.01 wt % water; and 0-50 wt % co-solvent and non-flammable non-chlorine-containing organic dry cleaning solvent. According to another aspect of the present invention, a continuous dry cleaning process is provided, comprising: a) a non-aqueous dry cleaning step in which the article is contacted with a non-aqueous dry cleaning composition comprising 0.001-10 wt % of a surfactant; 0-0.01 wt % of water; 0-50 wt % of a co-solvent and a non-flammable non-chlorine-containing organic dry cleaning solvent; and b) at least one low-aqueous dry cleaning step in which the article is contacted with a low-aqueous dry cleaning composition comprising 0.001-10 wt % of a cleaning-effective amount of an acidic surfactant; 0.01-50 wt % of water; 0-50 wt % of a co-solvent; and a non-flammable non-chlorine-containing organic dry cleaning solvent, and optionally at least one rinsing step in which the article is contacted with a rinsing composition comprising 0-0.0001 wt % of a surfactant; 0-10 wt % of water; and 0-50 wt % of a co-solvent and a non-flammable non-chlorine-containing organic dry cleaning solvent.

Depending on the cleaning desired, the low aqueous and non-aqueous compositions may be used in any order. However, in some instances, it may be preferred to contact the article with a non-aqueous composition before the low aqueous dry cleaning composition. In fact, the low aqueous dry cleaning step may precede or follow various other steps, such as regeneration, garment care treatment and/or rinsing steps, and indeed any other steps known to those skilled in the art.

Some forms of the invention may be particularly suitable for cleaning laundry stained with household staining materials selected from the group including edible oils, particulate soils, and mixtures thereof. Thus, according to one aspect, the dry cleaning process preferably comprises contacting the laundry stained with household staining materials selected from edible oils, particulate soils, and mixtures thereof with a dry cleaning composition. Particulate soil stains typically include any particulate matter that may be stained on clothing, such as grime, mud, sand, charcoal, cosmetics, deodorants, toothpaste, as well as corroded iron particles and mixtures thereof. Edible oils typically include edible fats and oils of animal or vegetable origin, such as lard, sunflower oil, soybean oil, olive oil, palm oil, peanut oil, rapeseed oil, and mixtures thereof.

Generally, articles such as clothing are cleaned by contacting the articles with a cleaning-effective amount of a dry cleaning composition according to one aspect of the present invention for a period of time effective to clean the articles or otherwise remove stains. Preferably, the laundry is immersed in the dry cleaning composition. The amount of dry cleaning composition used and the amount of time the composition is in contact with the articles can vary based on the equipment and the number of articles being cleaned. Normally, a dry cleaning process will include at least one step of contacting the articles with a dry cleaning composition according to the first aspect of the present invention and at least one step of rinsing the articles with a fresh charge of dry cleaning solvent. The rinse composition will usually be composed primarily of solvent, although cleaning agents may be added if desired.

In some aspects of the invention, an in situ formulation of the dry cleaning composition may be included in the pretreatment composition. After the laundry is pretreated with the pretreatment composition, the pretreated laundry is contacted with the remaining ingredients of the dry cleaning composition, thereby compounding the dry cleaning composition in situ. The pretreatment step may be performed manually outside the drum of the cleaning machine, or mechanically inside the drum as part of the pretreatment step. If the laundry is immersed in the dry cleaning composition when it is contacted with all the ingredients that make up the final dry cleaning composition, the pretreatment step itself may not require immersion, i.e., it may be limited to treating only the dyed areas. For example, if the dry cleaning composition includes a dry cleaning solvent, water, and a surfactant, the dyed areas of the laundry may be pretreated with a premix of water and surfactant by a manual or automated process. After an effective pretreatment time has elapsed, the laundry may be contacted with the remaining ingredients in the drum. The remaining dry cleaning ingredients may include a dry cleaning solvent (and optionally additional water and/or cleaning agents) to produce at least one dry cleaning composition in situ according to this aspect of the invention. Typically, the pretreatment time will be at least 5 seconds, but may be less than a day, preferably less than an hour, and more preferably less than 30 minutes. The pretreatment composition may be formulated to treat specific stains. For example, a cleaning effective amount of proteases and other enzymes may be included to treat proteinaceous stains. In another embodiment, the complete dry cleaning composition is premixed in a separate premix compartment. For example, if the dry cleaning composition includes a dry cleaning solvent, a surfactant, and water, these may be premixed in a separate compartment before the dry cleaning composition is contacted with the laundry. In some embodiments, such a premix is in the form of an emulsion or microemulsion. Forming a premix, for example, a water-in-oil emulsion, may be effected by any number of suitable procedures. For example, an aqueous phase containing a cleaning effective amount of surfactant may be contacted with the solvent phase by metered injection immediately prior to placing these components in the mixing device. Preferably, a metered amount is maintained so that the desired solvent/water ratio remains relatively constant. Mixing devices suitable for this practice include, for example, pump assemblies or in-line static mixers, centrifugal or other types of pumps, colloid or other types of mills, rotary mixers, ultrasonic mixers, and other means for dispersing one liquid into another. In some embodiments, immiscible liquids may be used to provide sufficient agitation to form an emulsion or pseudoemulsion.

These static mixers include devices through which the emulsion passes at high speeds and is subjected to rapid changes in direction and/or diameter of the channels that make up the interior of the mixer. This results in pressure losses that are a factor in obtaining the correct emulsion in terms of droplet size and stability.

In one variant of the method of the invention, the mixing step is, for example, continuous. The procedure consists of mixing the solvent and the emulsifier in a first step, and mixing and emulsifying the premix with water in a second step. In another variant of the method of the invention, provision is made for carrying out the above steps in a continuous manner.

The premix may be carried out at room temperature, which is also the temperature of the fluids and raw materials used.
Batch processes such as overhead mixers, or continuous processes such as two-liquid coextrusion nozzles, in-line injectors, in-line mixers, or in-line screens can be used to make the emulsion. The size of the emulsion composition in the final composition can be adjusted by changing the mixing speed, mixing time, mixing device, and viscosity of the aqueous solution. In general, emulsions with larger droplet sizes can be produced by reducing the mixing speed, decreasing the mixing time, decreasing the viscosity of the aqueous solution, or using a mixing device that generates lower shear forces during mixing. Particularly preferred is an ultrasonic mixer. It is understood that although the above description refers to the addition of surfactants, it can also be applied to the addition of cleaning agents.

1. Solvents In general, dry cleaning solvents are usually non-flammable non-chlorine-containing organic dry cleaning solvents. Although the term dry cleaning solvent is used in the singular, it must be noted that mixtures of solvents may also be used. Thus, the singular must be interpreted as including the plural and vice versa. Due to typical environmental issues associated with chlorine-containing solvents, the solvent preferably does not contain Cl atoms. In addition, the solvent must not be flammable, such as most petroleum or mineral spirits, which have typical flash points as low as 20°C or less. The term non-flammable is intended to describe dry cleaning solvents that have a flash point of at least 37.8°C, more preferably at least 45°C, and most preferably at least 50°C. The flash point limit of at least 37.8°C for non-flammable liquids is defined in the NFPA 30 Flammable and Combustible Liquids Code, discussed by the National Fire Protection Association, Massachusetts, USA, 1996 edition. The preferred test method for determining the flash point of a solvent is the standard test as described in NFPA 30. One class of solvents is the fluorinated organic dry cleaning solvents, including hydrofluorocarbons (HFCs) and hydrofluoroethers (HFEs). More preferred, however, are non-flammable non-halogenated solvents such as siloxanes (see below). It should be noted that mixtures of different dry cleaning solvents may also be used.

Some solvents are non-ozone depleting, and a useful common definition for Ozone Depletion Potential is defined by the US Environmental Protection Agency: Ozone Depletion Potential is the ratio of a chemical's effect on the ozone compared to the effect of a similar mass of CFC-11. The ODP of CFC-11 is therefore defined as 1.0.

Hydrofluorocarbons may be used as solvents, one suitable hydrofluorocarbon solvent being represented by the formula C,H,F(2x+2-y), where x is 3 to 8 and y is 1 to 6, and the molar ratio of F/H in the hydrofluorocarbon solvent is greater than 1.6. Preferably, x is 4 to 6, and most preferably, x is 5 and y is 2. Particularly suitable are hydrofluorocarbon solvents selected from the isomers of decafluoropentane and mixtures thereof. Particularly useful is 1,1,1,2,2,3,4,5,5,5-decafluoropentane. E. I. Du Pont De Nemours and Company sells this compound under the name Vertrel XF™.

Hydrofluoroethers (HFEs) suitable for use in the present invention are generally low polarity compounds containing minimal amounts of carbon, fluorine, hydrogen, and catenary (i.e., chain-like) oxygen atoms. HFEs may optionally contain additional catenary heteroatoms such as nitrogen and sulfur. HFEs have molecular structures that may be linear, branched, or cyclic, or combinations thereof (e.g., alkylcycloaliphatic), are preferably free of ethylenic unsaturation, and have a total of about 4 to about 20 carbon atoms. Such HFEs are known and readily available as either essentially pure compounds or mixtures. Preferred hydrofluoroethers may have boiling points in the range of about 40° C. to about 275° C., preferably about 50° C. to about 200° C., and more preferably about 50° C. to about 121° C. It is highly desirable for the hydrofluoroether to have no flash point. In general, if an HFE has a flash point, lowering the F/H ratio or decreasing the number of carbon-carbon bonds will each lower the flash point of the HFE (see International Publication No. 0026206).

Useful hydrofluoroethers include two varieties: segregated hydrofluoroethers and omega-hydrofluoroalkyl ethers. Structurally, segregated hydrofluoroethers contain at least one mono-, di-, or trialkoxy substituted perfluoroalkane, perfluorocycloalkane, perfluorocycloalkyl-containing perfluoroalkane, or perfluorocycloalkylene-containing perfluoroalkane compound.

Several siloxane solvents may also be advantageously used in the present invention. The siloxanes may be linear, branched, cyclic, or combinations thereof. One preferred branched siloxane is tris(trimethylsiloxyl)silane. Also preferred are linear and cyclic oligodimethylsiloxanes. One preferred class of siloxane solvents is represented by the formula:
R3-Si(-O-SiR2)w-R
where each R is independently selected from alkyl groups having 1 to 10 carbon atoms and w is an integer from 1 to 30. Preferably, R is methyl and w is 1 to 4, or more preferably w is 3 or 4.

Of the cyclic siloxanes, octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane are particularly effective. Very useful siloxanes are selected from the group consisting of decamethyltetrasiloxane, dodecamethylpentasiloxane and mixtures thereof.

Organic solvents suitable for dry cleaning include at least one solvent selected from the group consisting of nonafluoromethoxybutane, nonafluoroethoxybutane, and isomers of decafluoropentane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof. Some preferred organic dry cleaning solvents include those selected from the group consisting of octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, decamethyltetrasiloxane, dodecamethylpentasiloxane, and mixtures thereof.

The dry cleaning compositions of the present invention generally contain more than about 50% by weight of the organic dry cleaning solvent, preferably more than about 75% by weight, more preferably more than about 80% by weight, more preferably more than about 85% by weight, more preferably more than about 95% by weight, but preferably less than 100% by weight of the organic dry cleaning solvent by weight of the total dry cleaning composition. Such amounts can help improve drying times and maintain a high or no flash point. For rinsing or conditioning steps, the dry cleaning composition may contain at least 99% by weight of the organic dry cleaning solvent, and sometimes 100% by weight of the organic dry cleaning solvent by weight of the total dry cleaning composition.

In some instances, water may be used in the dry cleaning process and the amount of water is important. In those instances, the amount of water present in any step of the dry cleaning process is at a level such that laundry can be safely cleaned. This includes laundry that can only be dry cleaned. The amount of water present in low-aqueous dry cleaning compositions is preferably 0.01-50 wt% water, more preferably 0.01-10 wt%, more preferably 0.01-0.9 wt% water, or more preferably 0.05-0.8 wt%, or most preferably 0.1-0.7 wt% water by weight of the dry cleaning composition. The amount of water present in non-aqueous dry cleaning compositions is preferably 0-0.1 wt% water, or more preferably 0-0.01 wt%, or more preferably 0-0.001 wt%, and most preferably 0 wt% water by weight of the dry cleaning composition.

If the dry cleaning composition contains water, preferably the water to cloth ratio (w/w) (WCR) is less than 0.45, more preferably less than 0.35, more preferably less than 0.25, more preferably less than 0.2, most preferably less than 0.15, but usually greater than 0.0001, preferably greater than 0.001, more preferably greater than 0.01.

If the dry cleaning process includes more than one step, especially if the dry cleaning composition includes water and a solvent, this WCR is preferably applied to all steps of the dry cleaning process. However, the WCR may or may not be different for each step. It is also preferred that this WCR is applied to each step of the dry cleaning process where the LCR is greater than 1.

2. Co-solvent The composition of the present invention may contain one or more co-solvents. The purpose of the co-solvent in the dry cleaning composition of the present invention is often to increase the dissolving power of the dry cleaning composition on various soils. The co-solvent also allows the formation of a homogeneous solution containing the co-solvent, the dry cleaning solvent and the soil; or the co-solvent, the dry cleaning solvent and any cleaning agent. As used herein, a "homogeneous composition" is a single-phase composition, or a composition that appears to have only a single phase, such as a macroemulsion, microemulsion, or azeotrope. However, since azeotropes can be less robust, if a co-solvent is used, the dry cleaning composition is preferably a non-azeotrope.

Useful cosolvents of the present invention are soluble in dry cleaning solvents or water, are compatible with typical cleaning agents, and can enhance the solubility of hydrophilic composite dyes and oils typically found in dyeing garments, such as vegetable oils, mineral oils, or animal oils. Any cosolvent or cosolvent mixture meeting the above criteria may be used.

Useful co-solvents include, for example, alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, fully or partially halogenated derivatives thereof and mixtures thereof. Preferably, the co-solvent is selected from the group consisting of alcohols, alkanes, alkenes, cycloalkanes, ethers, esters, cyclic amides, aromatics, ketones, fully or partially halogenated derivatives thereof and mixtures thereof. Representative examples of cosolvents that may be used in the dry cleaning compositions of the present invention include methanol, ethanol, isopropanol, t-butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol monobutyl ether, trans-1,2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, N-alkylpyrrolidones (such as N-methylpyrrolidone and N-ethylpyrrolidone), methyl isobutyl ketone, naphthalene, toluene, trifluorotoluene, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, and perfluoro-2-butyloxacyclopentane.

Preferably, the co-solvent is present in the compositions of the present invention in an effective amount by weight to form a homogenous composition with the other dry cleaning solvent(s), such as an HFE. The effective amount of co-solvent will vary depending on which co-solvent or co-solvent blend is used and the other dry cleaning solvent(s) used in the composition. However, the preferred maximum amount of any individual co-solvent present in the dry cleaning composition must be low enough to keep the dry cleaning composition non-flammable as defined above.

Generally, the co-solvent may be present in the compositions of the present invention in an amount of about 1 to 50% by weight, preferably about 5 to about 40% by weight, and more preferably about 10 to about 25% by weight. In some instances, the co-solvent may be present in an amount of about 0.01% by weight of the total dry cleaning composition.

3. Surfactants The present invention relates to a surfactant having the formula 1:

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C ₁ -C ₆ alkyl, and an optional counterion may be associated with the compound, and if present, the counterion may be selected from the group consisting of chloride, bromide, and iodide.

The dry cleaning compositions of the present invention may utilize many types of cyclic, linear, or branched surfactants known in the art, both fluorinated and non-fluorinated. Preferred solvent-compatible surfactants include nonionic, anionic, cationic, and zwitterionic surfactants having at least 4 carbon atoms, but preferably less than 200 carbon atoms, or more preferably less than 90 carbon atoms, as described below. Solvent-compatible surfactants typically have a solvent-compatible moiety that increases the solubility of the surfactant in the dry cleaning solvent/composition. Effective surfactants contain one or more polar hydrophilic groups and one or more dry cleaning solvent-compatible moieties and may have at least 4 carbon atoms so that the surfactant is soluble in said dry cleaning solvent/composition. It is preferred that the surfactant is soluble in the dry cleaning composition, i.e., at 20° C., at least up to the amount of surfactant used in the dry cleaning composition. The composition may contain one surfactant or a mixture of surfactants depending on the desired cleaning and fabric care. One preferred surfactant is an anionic surfactant. Another preferred surfactant is a cationic surfactant.

The polar hydrophilic group Z can be nonionic, ionic (i.e., anionic, cationic, or amphoteric), or a combination thereof. Exemplary nonionic moieties include polyoxyethylene and polyoxypropylene moieties. Exemplary anionic moieties include carboxylate, sulfonate, sulfate, or phosphate moieties. Exemplary cationic moieties include quaternary ammonium, protonated ammonium, imidazoline, amine, diamine, sulfonium, and phosphonium moieties. Exemplary amphoteric moieties include betaine, sulfobetaine, aminocarboxyl, amine oxide, and various other combinations of anionic and cationic moieties. Particularly suitable surfactants include at least one polar hydrophilic group Z that is an anionic moiety, and the counterion can be as described below.

The polar hydrophilic group Z is preferably selected from the group including -SOM, -SOM, -POM, -POM, -COM and mixtures thereof (wherein each M may be independently selected from groups including H, NR, Na, K and Li, and each R is independently selected from H and C alkyl radicals, but is preferably H). Preferably M is H, although in some instances salts may be used.

The surfactant may be fluorinated or, more preferably, a fluorinated acid. Suitable fluorosurfactants in most instances have the formula (1):
(Xf)n(Y)m(Z)p
and contains one, two or more fluorinated radicals (Xf) and one or more polar hydrophilic groups (Z), where the radicals and the polar hydrophilic groups are usually (but not necessarily) linked to each other by one or more suitable linking groups (Y). Preferably, n and p are integers independently selected from 1 to 4, and m is selected from 0 to 4. When the surfactant comprises more than one Xf, Y or Z, each of Xf, Y and Z may be the same or different. The polar hydrophilic group may be linked to Y by a covalent bond or to Xf in the absence of Y.

Fluorinated radicals Xf can generally be linear or cyclic, saturated or unsaturated, aromatic or non-aromatic radicals, preferably having at least 3 carbon atoms. The carbon chain may be linear or branched and may contain heteroatoms such as oxygen or sulfur, but preferably does not contain nitrogen. Xf is aliphatically saturated. Fully fluorinated Xf radicals are preferred, although hydrogen or chlorine may be present as substituents, provided that a maximum of one atom of either is present for every two carbon atoms, and preferably the radical contains at least a terminal perfluoromethyl group. Radicals containing only about 20 carbon atoms or less are preferred, since larger radicals usually imply less efficient fluorine utilization. Particularly suitable Xf groups can be based on perfluorinated carbon: CF, where n is 1-40, preferably 2-26, most preferably 2-18, or on oligomers of hexafluoropropylene oxide: ICF(CF)-CF.O, where n is 1-30. A suitable example of the latter is Krytox I™ 157, specifically sold under the name Krytox I™ 157 FSL by E. l DuPont de Nemours and Co.

The linking group Y is selected from groups such as alkyl, alkylene, alkylene oxide, arylene, carbonyl, ester, amide, ether oxygen, secondary or tertiary amine, sulfonamido alkylene, carboxamido alkylene, alkylenesulfonamido alkylene, alkyleneoxyalkylene or alkylenethioalkylene, or mixtures thereof. In one preferred embodiment, Y is (CH ₂ ) or (CH ₂ )O, where t is 1 to 10, preferably 1 to 6, most preferably 2 to 4. Alternatively, Y may be absent, in which case Xf and Z are directly linked by a covalent bond.

Another suitable class of surfactants is represented by formula (2):
(Xh)n(Y)m(Z)p
where Xh is a non-fluorinated radical and (Y), (Z), n, m and P are as described in Formula 1. Xh may be a linear, branched or cyclic, saturated or unsaturated, aromatic or non-aromatic radical, preferably having at least 4 carbon atoms. Xh preferably comprises a hydrocarbon radical. When Xh is a hydrocarbon, the carbon chain may be linear, branched or cyclic and may contain heteroatoms such as oxygen, nitrogen or sulfur, although nitrogen is not preferred in some instances. In some embodiments, Xh is aliphatically saturated. Radicals containing no more than about 24 carbon atoms are preferred.

One preferred surfactant is an acidic surfactant. Some surfactants include anionic surfactants. Anionic surfactants are generally known in the art and include, for example, alkylaryl sulfonates (e.g., alkylbenzene sulfonates, etc.), alkylaryl sulfonic acids (e.g., sodium and ammonium salts of toluene-, xylene-, and isopropylbenzene sulfonic acid, etc.), sulfonated amines and sulfonated amides (e.g., amidosulfonates, etc.), carboxylated alcohol and carboxylated alkylphenol ethoxylates, diphenyl sulfonates, fatty esters, isethionates, lignin-based surfactants, olefin sulfonates (e.g., RCHCHSO ₃ , etc.), and the like. Na (where R is C10-C16), phosphorus based surfactants, protein based surfactants, sarcosine based surfactants (such as N-acylsarcosinates such as sodium N-lauroyl sarcosinate), sulfates and sulfonates of oils and/or fatty acids, sulfates and sulfonates of ethoxylated alkylphenols, sulfates of alcohols, sulfates of ethoxylated alcohols, fatty ester sulfates, sulfates of aromatic or fluorine containing compounds, sulfosuccinamates, sulfosuccinates (such as diamyl-, dioctyl-, and diisobutylsulfosuccinate), taurates, and sulfonic acids. Examples of suitable non-fluorinated anionic surfactants include Crodafos™ 810A (ex Croda).

In addition to acidic surfactants, other classes of surfactants may be used. Suitable surfactants include, but are not limited to, nonionic and cationic surfactants. Compounds suitable for use as nonionic surfactants in the present invention are those that do not carry a isolated charge when dissolved in an aqueous medium. Nonionic surfactants are generally known in the art and include, for example, alkanolamides (such as coconut, lauric, oleic and stearic acid monoethanolamide, diethanolamide and monoisopropanolamide), amine oxides (such as polyoxyethylene ethanolamide and polyoxyethylene propanolamide), polyalkylene oxide block copolymers (such as poly(oxyethylene-co-oxypropylene)), ethoxylated alcohols (such as isostearyl polyoxyethylene alcohol, lauryl, cetyl, stearyl, oleyl, tridecyl, trimethylnonyl, isodecyl, tridecyl, etc.), ethoxylated alkylphenols (such as nonylphenyl ethoxylated amines and ethoxylated amides), ethoxylated fatty acids, ethoxylated fatty esters and ethoxylated fatty oils (such as mono- and diesters of lauric, isostearic, pelargonic, oleic, coconut, stearic and ricinoleic acids, as well as castor oil and tall oil, and other oils), fatty esters, fluorocarbon-containing materials, glycerol esters (such as glycerol monostearate, glycerol monolaurate, glycerol dilaurate, glycerol monoricinoleate, and glycerol oleate), glycol esters (such as propylene glycol monostearate, ethylene glycol monostearate, ethylene glycol distearate, diethylene glycol monolaurate, diethylene glycol monolaurate, diethylene glycol monooleate, and diethylene glycol stearate), lanolin-based surfactants, monoglycerides, phosphate esters, polysaccharide ethers, propoxylated fatty acids, propoxylated alcohols, and propoxylated alkyl phenols, protein-based organic surfactants, sorbitan-based surfactants (such as sorbitan oleate, sorbitan monolaurate, and sorbitan palmitate), sucrose esters and glucose esters, and thio- and mercapto-based surfactants.

Some other suitable nonionic surfactants include polyethylene oxide condensates of nonylphenol and myristyl alcohol. Kasprzak, U.S. Pat. No. 4,685,930, and b) fatty alcohol ethoxylates R-(OCH ₂ CH ₂ )OH, where a-1 to 100, typically 1 to 30, and R=hydrocarbon residues of 8 to 20 carbon atoms, typically linear alkyl. Examples include polyoxyethylene lauryl ether with 4 to 10 oxyethylene groups; polyoxyethylene cetyl ether with 2, 6, or 10 oxyethylene groups; polyoxyethylene stearyl ether with 2, 5, 15, 20, 25, or 100 oxyethylene groups; polyoxyethylene (2),(10) oleyl ether with 2 or 10 oxyethylene groups. Commercially available examples include, but are not limited to, BRIJ® and NEODOL. See also Hill et al., U.S. Pat. No. 6,013,683. Other suitable non-ionic surfactants include Tweens™.

Suitable cationic surfactants include, but are not limited to, dialkyldimethylammonium salts having the formula R''R''N''(CH)X, where R' and R'' are each independently selected from a group consisting of a hydrocarbon containing a moiety containing 1 to 30 carbon atoms, or a group consisting of a hydrocarbon derived from tallow, coconut oil, or soybean, and X-Cl, I, or Br. Examples include didodecyldimethylammonium bromide (DDAB), dihexadecyldimethylammonium chloride, dihexadecyldimethylammonium bromide, dioctadecyldimethylammonium chloride, dieicosyldimethylammonium chloride, didocosyldimethylammonium chloride, dicoconut dimethylammonium chloride, ditallowdimethylammonium bromide (DTAB). Commercially available examples include, but are not limited to, ADOGEN, ARQUAD, TOMAH, VARIOUAT. See also U.S. Patent No. 6,013,683 to Hill et al.

These and other surfactants suitable for use with organic dry cleaning solvents as adjuvants are well known in the art and are described in more detail in Kirk Othmer's Encyclopaedia of Chemical Technology, 3rd Ed., Vol. 22, pp. 360-379, "Surfactants and Detersive Systems," incorporated herein by reference. Further suitable nonionic detergent surfactants are generally disclosed in U.S. Patent No. 3,929,678, filed December 20, 1975, to Laughlin et al., at column 13, line 14 to column 16, line 6, incorporated herein by reference. Other suitable detergent surfactants are generally disclosed in WO-A-0246517.

The surfactant or surfactant mixture is present in a cleaning effective amount. A cleaning effective amount is that amount required for the desired cleaning. This will depend, for example, on the number of articles, the level of soil loading, and the volume of dry cleaning composition used. Effective cleaning has been observed when the surfactant is present at at least 0.001 wt % to 10 wt % by weight of the dry cleaning composition. More preferably, the surfactant is present at 0.01 to 3 wt %, or more preferably 0.05 to 0.9 wt % by weight of the dry cleaning composition. More preferably, the surfactant is present at 0.1 to 0.8 wt %, more preferably 0.3 to 0.7 wt % by weight of the dry cleaning composition.

The dry cleaning composition may contain one or more optional cleaning agents. Cleaning agents include any agent suitable for enhancing the cleaning, appearance, condition and/or care of garments. Generally, cleaning agents may be present in the compositions of the present invention in an amount of about 0-20 wt %, preferably 0.001 wt % to 10 wt %, more preferably 0.01 wt % to 2 wt % by weight of the total dry cleaning composition.

Some suitable cleaning agents include the following compounds: builders, enzymes, bleach activators, bleach catalysts, bleach boosters, bleaching agents, alkalinity sources, antimicrobials, colorants, fragrances, pro-perfumes, finishing aids, lime soap dispersants, malodor suppressants for the composition, odor neutralizers, polymeric dye transfer inhibitors, crystal growth inhibitors, photobleaching agents, heavy metal ion sequestrants, discoloration inhibitors, antimicrobials, antioxidants, anti-redeposition agents, soil resistant polymers, electrolytes, pH adjusters, thickeners, abrasives, divalent or trivalent ions, metal ion salts, enzyme stabilizers, corrosion inhibitors, diamines or polyamines and/or alkoxylates thereof, foam stabilizing polymers, processing aids, fabric softeners, optical enhancers, hydrotropes, foam or foam suppressants, foam or foam boosters, fabric softeners, antistatic agents, dye fixatives, dye abrasion inhibitors. Some suitable cleaning agents include, but are not limited to, anti-bleaching agents, anti-wrinkle agents, anti-wrinkle agents, stain repellents, sunscreen agents, anti-fading agents, and mixtures thereof.

EXAMPLES Nuclear magnetic resonance (NMR) spectroscopy was performed on a Bruker 500 MHz spectrometer. Critical micelle concentration (CMC) was measured at 23°C using a tensiometer (DCAT11, DataPhysics Instruments GmbH) equipped with a Pt-Ir plate by the Wilhelmy plate method. Dynamic surface tension was determined at 23°C using a bubble pressure tensiometer (Kruss BP100, Kruss GmbH). Contact angles were determined with an optical contact angle goniometer (OCA15 Pro, DataPhysics GmbH) equipped with a digital camera.

Example 1a:
Synthesis of 6-(dimethylamino)-N-(3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)hexanamide (surfactant 1) and 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-aminium salt (surfactant 2)

Example 1b:
Determination of the Critical Micelle Concentration (CMC) of Surfactant 2 The critical micelle concentration (CMC) of surfactant 2 was tested with chloride counterion and determined to be approximately 2 mmol. The minimum surface tension plateau value achievable with this surfactant is approximately 23 mN/m. Figure 1 is a plot of these results, showing surface tension versus concentration.

Example 2a:
Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N,N-trimethyl-6-oxohexane-1-aminium iodide (Surfactant 3)

Surfactant 1 ( _1.00 g, 2.02 mmol, 1 equiv.) was dissolved in acetonitrile (10 ml) in a 100 ml round bottom flask. _Na2CO3 (0.26 g, 2.42 mmol, 1.2 equiv.) was then added and the mixture was stirred for 10 min. Methyl iodide (0.377 ml, 6.06 mmol, 3 equiv.) was added and the reaction was heated at 40° C. for 24 h. The cooled reaction mixture was filtered and the solvent removed under vacuum to give surfactant 3 as a slightly yellow solid in quantitative yield. ^-H NMR (500 MHz, DMSO) δ 0.09 (s, 27H), 0.38-0.42 (m, 2H), 1.23-1.26 (m, 2H), 1.37-1.40 (m, 2H), 1.52-1.55 (m, 2H), 1.65-1.69 (m, 2H), 2.08 (t, J=7.4 Hz, 2H), 2.99 (dd, J=13, 6.9 Hz, 2H), 3.04 (s, 9H), 3.24-3.33 (m, 2H).

The pure product is soluble in water and has surfactant properties. The halogen anion may be obtained directly from the N-alkylation reaction or other desired negative counterions may be obtained by anion exchange.

Example 2b:
Determination of the Physical Properties of Surfactant 3 The critical micelle concentration (CMC) of surfactant 3 was measured. From the surface tension change and concentration in water, the CMC was determined to be about 1.6 mmol. The plateau value of the minimum surface tension achievable by this surfactant was about 20 mN/m, indicating that this surfactant has outstanding interfacial activity. These results are plotted as surface tension versus concentration in Figure 2.

The dynamic surface tension of surfactant 3 was determined with a bubble pressure tensiometer, which measures the change in surface tension of a freshly created air-water interface with time. Figure 3 shows a plot of the results of surface tension versus time, demonstrating that surfactant 3 completely saturated the interface in less than 500 ms, and was exceptionally rapid with respect to interfacial adsorption.

The formulation containing only surfactant has exceptional wetting properties in addition to the ability of surfactant 3 to reduce both interfacial and surface tension. Hydrophobic substrates such as polyethylene and polypropylene exhibit total surface wetting with a contact angle of 0°. For oleophobic and hydrophobic substrates such as Teflon, the measured contact angle was an extremely low 10.5° (Table 2).

Example 3a:
Synthesis of 6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxane-3-yl)propyl)amino)-N,N-dimethyl-6-oxohexane-1-amine oxide (surfactant 4)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was added to distilled water (80 mL) in a 100 mL round bottom flask followed by 50% hydrogen peroxide (1.15 ml, 20.2 mmol, 10 equiv.). The reaction was refluxed for 12 h and then concentrated under vacuum. The residue was washed three times with acetone to give surfactant 4 in 99% yield. ^1H NMR (500MHz, DMSO) δ 0.09 (s, 27H), 0.38-0.44 (m, 2H), 1.21-1.25 (m, 2H), 1.35-1.42 (m, 2H), 1.50-1.55 (m, 2H), 1.71-1.75 (m, 2H), 2.05-2.08 (m, 2H), 2.97-3.00 (m, 2H), 3.01 (s, 9H), 3.11-3.14 (m, 2H).

Example 3b:
Determination of the Physical Properties of Surfactant 4 The critical micelle concentration (CMC) of surfactant 4 was measured. From the surface tension change and concentration in water, the CMC was determined to be about 0.49 mmol. The plateau value of the minimum surface tension achievable by this surfactant was about 20 mN/m, indicating that this surfactant has outstanding interfacial activity. These results are plotted as surface tension versus concentration in Figure 4.

The dynamic surface tension of surfactant 4 was determined with a bubble pressure tensiometer. Figure 5 shows a plot of the results of surface tension versus time, demonstrating that surfactant 4 completely saturated the freshly created air-water interface within 1 second and was rapid with respect to interfacial adsorption.

Formulations containing only surfactant 4 at concentrations between 1 and 100x CMC have exceptional wetting properties in addition to surfactant 4's ability to reduce both interfacial and surface tension. For example, a solution of surfactant 4 in water at a concentration of 10x CMC exhibits a contact angle of 0° on hydrophobic substrates such as polyethylene and polypropylene, and 10.6° on oleophobic and hydrophobic substrates such as Teflon. These contact angles are extremely low compared to the contact angles of water on the same substrates (Table 3).

Example 4a:
Synthesis of 4-((6-((3-(1,1,1,5,5,5-hexamethyl-3-((trimethylsilyl)oxy)trisiloxan-3-yl)propyl)amino)-6-oxohexyl)dimethylammonio)butane-1-sulfonate (Surfactant 5)

Surfactant 1 (1.00 g, 2.02 mmol, 1 equiv.) was added to ethyl acetate (EtOAc) (30 mL) in a 100 mL round bottom flask followed by 1,2-butanesultone (0.27 mL, 2.2 mmol, 1.1 equiv.). The reaction was refluxed for 12 h, after which the solvent was removed and the resulting white waxy solid was washed with acetone to give surfactant 5 in 50% yield. ^1H NMR (500 MHz, DMSO) δ 0.10 (s, 27H), 0.38-0.46 (m, 2H), 1.23-1.27 (m, 2H), 1.37-1.68 (m, 10H), 1.73-1.78 (m, 2H), 2.45-2.48 (m, 2H), 2.97-3.01 (m, 8H), 3.18-3.21 (m, 2H), 3.23-3.27 (m, 2H).

Example 4b:
Determination of the Physical Properties of Surfactant 5 The critical micelle concentration (CMC) of surfactant 5 was measured. From the surface tension change and concentration in water, the CMC was determined to be about 0.39 mmol. The plateau value of the minimum surface tension achievable by this surfactant was about 21 mN/m, indicating that this surfactant has outstanding interfacial activity. These results are plotted as surface tension versus concentration in FIG. 6.

The dynamic surface tension of surfactant 5 was determined with a bubble pressure tensiometer. Figure 7 shows a plot of the results of surface tension versus time, demonstrating that surfactant 5 completely saturated the freshly created air-water interface within 1 second and was rapid with respect to interfacial adsorption.

Finally, a solution of surfactant 5 in water at a concentration of 10x CMC exhibits a contact angle of 0° on hydrophobic substrates such as polyethylene and polypropylene, and 10.2° on oleophobic and hydrophobic substrates such as Teflon. These contact angles are extremely low compared to the contact angle of water on the same substrates (Table 4).

Example 5:
Soaps containing two or more inventive surfactants Detergent formulations containing soap, fully saturated lauric soap granules based on Prifac 5808 from Uniqema, a first inventive surfactant and a non-ionic inventive surfactant. All formulations contain 1.008 g/l surfactant and 0.25-0.67 soap. Water was conditioned with a mixture _{of CaCl2.2H2O} and _MgCl.H2O to achieve calcium to magnesium ratio.

Example 6
Dry Cleaning Formulations Laundry is contacted with the following low aqueous dry cleaning composition A (see Table 1) using a liquid to fabric ratio of 13 and agitated for 15 minutes at 20° C. The dry cleaning composition is then removed and the laundry is rinsed with a rinse composition comprising clean dry cleaning solvent. The experiment is repeated with the following low aqueous dry cleaning compositions B through F (see Table 1) using a liquid to fabric ratio of 5.

The first aspect of the present invention is a compound represented by the formula 1

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate; n is an integer from 1 to 12; the terminal nitrogen is optionally further substituted with R ³ , where R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C ₁ -C ₆ alkyl; an optional counterion, if present, associated with said compound, selected from the group consisting of chloride, bromide, and iodide; and at least one detergent and/or at least one soap.

A second aspect of the invention includes the first aspect of the invention, in which the at least one detergent or soap is selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, and zwitterionic detergents.

A third aspect of the invention includes the first and second aspects of the invention in which the soap has the general formula: (RCO ₂ ⁻ ) _n M ⁿ⁺ where R contains an alkyl group, M is a metal, and ⁿ⁺ is either +1 or +2.

A fourth aspect of the invention includes the first to third aspects of the invention, further comprising at least one builder.
A fifth aspect of the invention includes the first to fourth aspects of the invention, wherein the at least one builder is at least one compound selected from the group consisting of tripolyphosphates, nitroacetates, zeolites, calcites/carbonates, citrates or polymers, sodium, pyrophosphates, orthophosphates, sodium aluminosilicates, inorganic salts of alkali agents, inorganic salts of alkali metals, sulfates, silicates, and metasilicates.

A sixth aspect of the invention includes any of the first to fifth aspects of the invention, further comprising at least one bleaching agent.
A seventh aspect of the invention includes the sixth aspect of the invention, wherein the at least one bleaching agent is at least one compound selected from the group consisting of metal borates, persalts, peroxyacids, percarbonates, perphosphates, persilicates, persulfates, sodium hypochlorite, chlorine dioxide, hydrogen peroxide, sodium percarbonate, sodium perborate, peroxyacetic acid, benzoyl peroxide, potassium persulfate, potassium permanganate, sodium dithionite.

An eighth aspect of the invention includes the first to seventh aspects of the invention, further comprising at least one enzyme.
A ninth aspect of the invention includes the eighth aspect of the invention, wherein the at least one enzyme is selected from the group consisting of proteases, amylases, cellulases, oxidases, mannanases, peroxidases and lipases.

A tenth aspect of the present invention includes the first to ninth aspects of the present invention, further comprising at least one polymer.
An eleventh aspect of the invention includes the tenth aspect of the invention, wherein the at least one polymer is at least one compound selected from the group consisting of polymers of methacrylamide; polymers of ethylenically unsaturated monomers, N,N-dialkylaminoalkyl methacrylates, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkyl acrylamides, N,N-dialkylaminoalkyl methacrylamides, methacrylamidoalkyl trialkyl ammonium salts, acrylamidoalkyl trialkyl ammonium salts, vinylamines, vinyl imidazoles, quaternary vinyl imidazoles, and diallyl dialkyl ammonium salts; diallyl dimethyl ammonium salts, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, [2-(methacryloylamino)ethyl] trimethyl ammonium salts, N,N-dimethylaminopropyl acrylamide, N,N-dimethylaminopropyl methacrylamide, acrylamidopropyl trimethyl ammonium salts, methacrylamidopropyl trimethyl ammonium salts, and quaternary vinyl imidazoles.

The twelfth aspect of the present invention is a compound represented by formula 1.

wherein R ¹ and R ² may be the same or different and may comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
n is an integer from 1 to 12;
the terminal nitrogen is optionally further substituted with ^R3 , where ^R3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and _C1 - _C6 alkyl;
an optional counterion, if present, associated with said compound, selected from the group consisting of chloride, bromide, and iodide;
At least one solvent;
The composition further comprises at least one formulation for dry cleaning comprising:

A thirteenth aspect of the present invention includes the twelfth aspect of the present invention, in which the at least one solvent is at least one compound selected from the group consisting of perchloroethylene, a hydrocarbon, trichloroethylene, decamethylcyclopentasiloxane, dibutoxymethane, and n-propyl bromide.

A fourteenth aspect of the present invention includes the twelfth and thirteenth aspects of the present invention, further comprising at least one co-solvent.
A fifteenth aspect of the present invention relates to a process for preparing a fluoropolymerizable composition comprising at least one co-solvent selected from the group consisting of alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, methanol, ethanol, isopropanol, t-butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol ether, propylene ... and a fourteenth aspect of the present invention, which is at least one compound selected from the group consisting of ethylene glycol monobutyl ether, trans-1,2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, N-alkylpyrrolidones (N-methylpyrrolidone, N-ethylpyrrolidone, etc.), methyl isobutyl ketone, naphthalene, toluene, trifluorotoluene, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, and perfluoro-2-butyloxacyclopentane.

Claims (15)

Equation 1
wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
n is an integer from 1 to 12,
the terminal nitrogen may be further substituted with ^R3 , where ^R3 is selected from the group consisting of hydrogen, oxygen, hydroxyl, and _C1 - _C6 alkyl ;
an optional counterion associated with said surfactant compound , if present, selected from the group consisting of chloride, bromide, and iodide;
At least one detergent or at least one soap;
A cleaning formulation comprising: The formulation of claim 1, wherein the at least one detergent or soap is selected from the group consisting of anionic detergents, cationic detergents, nonionic detergents, and zwitterionic detergents. The soap has the general formula:
( _RCO2- ⁾ _nMn ⁺
2. The formulation of claim 1, having the formula: wherein R comprises an alkyl group, M is a metal, and n+ is either +1 or +2. The formulation of claim 1 further comprising at least one builder. The formulation of claim 4, wherein the at least one builder is at least one compound selected from the group consisting of tripolyphosphates, nitroacetates, zeolites, calcites/carbonates, citrates or polymers, pyrophosphates, orthophosphates, sodium aluminosilicates, inorganic salts of alkali agents, inorganic salts of alkali metals, sulfates, silicates, and metasilicates. The formulation of claim 1 further comprising at least one bleaching agent. The formulation of claim 6, wherein the at least one bleaching agent is at least one compound selected from the group consisting of metal borates, persalts, peroxyacids, percarbonates, perphosphates, persilicates, persulfates, sodium hypochlorite, chlorine dioxide, hydrogen peroxide, sodium percarbonate, sodium perborate, peroxyacetic acid, benzoyl peroxide, potassium persulfate, potassium permanganate, and sodium dithionite. The formulation of claim 1 further comprising at least one enzyme. The formulation of claim 8, wherein the at least one enzyme is selected from the group consisting of proteases, amylases, cellulases, oxidases, mannanases, peroxidases and lipases. The formulation of claim 1 further comprising at least one polymer. 11. The composition of claim 10, wherein the at least one polymer is at least one compound selected from the group consisting of polymers of methacrylamide; polymers of ethylenically unsaturated monomers, N,N-dialkylaminoalkyl methacrylates, N,N-dialkylaminoalkyl acrylates, N,N-dialkylaminoalkyl acrylamides, N,N-dialkylaminoalkyl methacrylamides, methacrylamidoalkyl trialkyl ammonium salts, acrylamidoalkyl trialkyl ammonium salts, vinylamines, vinyl imidazoles, quaternary vinyl imidazoles, and diallyl dialkyl ammonium salts; diallyl dimethyl ammonium salts, N,N-dimethyl aminoethyl acrylates, N,N-dimethyl aminoethyl methacrylates, [2-(methacryloylamino)ethyl] trimethyl ammonium salts, N,N-dimethyl aminopropyl acrylamides, N,N-dimethyl aminopropyl methacrylamides, acrylamidopropyl trimethyl ammonium salts, methacrylamidopropyl trimethyl ammonium salts, and quaternary vinyl imidazoles. Equation 1
wherein R ¹ and R ² may be the same or different and comprise at least one group selected from the group consisting of C ₁ -C ₆ alkyl, optionally C ₁ -C ₆ alkyl may comprise one or more of an oxygen, nitrogen, or sulfur atom or a group containing at least one of these atoms, and the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of hydroxyl, amino, amido, sulfonyl, sulfonate, carbonyl, carboxyl, and carboxylate;
n is an integer from 1 to 12,
the terminal nitrogen may be further substituted with R ³ , where R ³ is selected from the group consisting of hydrogen, oxygen, hydroxyl, and C ₁ -C ₆ alkyl ;
an optional counterion associated with said surfactant compound , if present, selected from the group consisting of chloride, bromide, and iodide;
At least one solvent;
4. A formulation for dry cleaning comprising: The formulation of claim 12, wherein the at least one solvent is at least one compound selected from the group consisting of perchloroethylene, a hydrocarbon, trichloroethylene, decamethylcyclopentasiloxane, dibutoxymethane, and n-propyl bromide. The formulation of claim 12 further comprising at least one co-solvent. The at least one co-solvent is selected from the group consisting of alcohols, ethers, glycol ethers, alkanes, alkenes, linear and cyclic amides, perfluorinated tertiary amines, perfluoroethers, cycloalkanes, esters, ketones, aromatics, methanol, ethanol, isopropanol, t-butyl alcohol, trifluoroethanol, pentafluoropropanol, hexafluoro-2-propanol, methyl t-butyl ether, methyl t-amyl ether, propylene glycol n-propyl ether, propylene glycol n-butyl ether, dipropylene glycol n-butyl ether, propylene glycol methyl ether, ethylene glycol monobutyl ether, trans-1,2-dichloroethylene, decalin, methyl decanoate, t-butyl acetate, ethyl acetate, glycol methyl ether acetate, ethyl lactate, diethyl phthalate, 2-butanone, 15. The formulation of claim 14, which is at least one compound selected from the group consisting of N-alkylpyrrolidone, methyl isobutyl ketone, naphthalene, toluene, trifluorotoluene, perfluorohexane, perfluoroheptane, perfluorooctane, perfluorotributylamine, and perfluoro-2-butyloxacyclopentane.

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